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Palladium‐Catalysed Cross‐Coupling Reactions Controlled by Noncovalent Zn⋅⋅⋅N Interactions
Author(s) -
Kadri Mohamed,
Hou Jingran,
Dorcet Vincent,
Roisnel Thierry,
Bechki Lazhar,
Miloudi Abdellah,
Bruneau Christian,
GramageDoria Rafael
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604780
Subject(s) - palladium , chemistry , zinc , non covalent interactions , reactivity (psychology) , catalysis , coupling reaction , supramolecular chemistry , heck reaction , polymer chemistry , halogen , covalent bond , photochemistry , organic chemistry , molecule , hydrogen bond , alkyl , medicine , alternative medicine , pathology
Non‐covalent interactions between halopyridine substrates and catalytically inert building blocks, namely zinc(II)–porphyrins and zinc(II)–salphens, influence the catalytic outcome of Suzuki–Miyaura and Mizoroki–Heck palladium‐catalysed cross‐coupling reactions. The weak Zn⋅⋅⋅N interactions between halopyridine substrates and zinc(II)‐containing porphyrins and salphens, respectively, were studied by a combination of 1 H NMR spectroscopy, UV/Vis studies, Job‐Plot analysis and, in some cases, X‐ray diffraction studies. Additionally, the former studies revealed unique supramolecular polymeric and dimeric rearrangements in the solid state featuring weak Br⋅⋅⋅N (halogen bonding), C−H⋅⋅⋅π, Br⋅⋅⋅π and π⋅⋅⋅π interactions. The reactivity of halopyridine substrates in homogeneous palladium‐catalysed cross‐coupling reactions was found to correlate with the binding strength between the zinc(II)‐containing scaffolds and the corresponding halopyridine. Such observation is explained by the unfavourable formation of inactive over‐coordinated halopyridine⋅⋅⋅palladium species. The presented approach is particularly appealing for those cases in which substrates and/or products deactivate (or partially poison) a transition‐metal catalyst.